Variation of M···H–C interactions in square-planar complexes of nickel(II), palladium(II), and platinum(II) probed by luminescence spectroscopy and X-ray diffraction at variable pressure

Stéphanie Poirier (1) , Hudson Lynn (1) , Christian Reber (2, 1) , Élodie Tailleur (3) , Mathieu Marchivie (3) , Philippe Guionneau (3) , Michael Probert (4)

1 Département de chimie [UdeM-Montréal]
2 UdeM - Université de Montréal
3 ICMCB - Institut de Chimie de la Matière Condensée de Bordeaux
4 Chemistry, School of Natural and Environmental Sciences

Luminescence spectra of isoelectronic square-planar d8 complexes with 3d, 4d, and 5d metal centers show d–d luminescence with an energetic order different from that of the spectrochemical series, indicating that additional structural effects, such as different ligand–metal–ligand angles, are important factors. Variable-pressure luminescence spectra of square-planar nickel(II), palladium(II), and platinum(II) complexes with dimethyldithiocarbamate ({CH3}2DTC) ligands and their deuterated analogues show unexpected variations of the shifts of their maxima. High-resolution crystal structures and crystal structures at variable pressure for [Pt{(CH3)2DTC}2] indicate that intermolecular M···H–C interactions are at the origin of these different shifts.

Domaines: Matériaux

Stéphanie Poirier, Hudson Lynn, Christian Reber, Élodie Tailleur, Mathieu Marchivie, et al.. Variation of M···H–C interactions in square-planar complexes of nickel(II), palladium(II), and platinum(II) probed by luminescence spectroscopy and X-ray diffraction at variable pressure. Inorganic Chemistry, 2018, 57 (13), pp.7713-7723. ⟨10.1021/acs.inorgchem.8b00724⟩. ⟨hal-01833179⟩